3, 3&#39; alkylenebis



3,3'ALKYLENEBIS(3,4-DIHYDRO-2H-1,3- BENZOXAZIN ES) Raymond H. Rigterink, Midland, Mich., assignor to The Dow Chemical Company, Midland, Mich., a corporation of Delaware No Drawing. Application May 6, 1957 Serial No. 657,047

7 Claims. (Cl. 260-244) This invention relates to 3,3-alkylenebis(3,4-dihydro- 2H-l,3-benzoxazines) having the formula In this and succeeding formulae, n is an integer from 2 to 6, inclusive and R represents alkyl or cyclohexyl. The expression alkyl is employed in the present specification and claims to refer to aliphatic hydrocarbon radicals containing from 1 to 8 carbon atoms, inclusive. These compounds are crystalline solids or liquids somewhat soluble in many common'organic solvents and of very low solubility in water. The new compounds are useful as parasiticides and are adapted to be employed in dust and liquid compositions for the control of many undesirable organisms such as Alternaria solani.

The new compounds may be prepared by causing a reaction between an alkylenediamine having the formula and formaldehyde, or a suitable formaldehyde yielding substance, to form an intermediate formaldehyde-amine condensation product. The intermediate product is then caused to react with a para substituted phenolic compound having the formula to form the desired product and water of reaction.

In carrying out the first step of the reaction, the alkylenediamine is intimately contacted with formaldehyde, or a formaldehyde yielding substance such as paraformaldehyde, and preferably in the presence of an inert solvent such as methanol, ethanol or dioxane as a reaction medium. The contacting of the reactants is carried out with stirring and cooling and at a temperature of from to 70 C. Good results are obtained when reacting one molecular proportion of the diamine with four molecular proportions of formaldehyde. The formaldehyde may be employed in any readily available form such as formalin, trioxane and paraformaldehyde. The amount of formaldehyde is calculated on the basis of the monomer unit.

In carrying out the second step of the reaction, the phenolic compound or a solution thereof in one of the above-named solvents is added portionwise to the reaction mixture, prepared as described above. In such operations, two molecular proportions of phenol are employed for each molecular proportion of diamine used in the preparation of the intermediate formaldehyde-amine "ice product. The reaction takes place smoothly at the temperature range of from 30 to 100 C. Upon completion of the reaction, the reaction mixture may be fractionally distilled under reduced pressure to remove the low boiling constituents and obtain the desired product as a liquid or crystalline residue. The desired product may be puritied in conventional fashion such as washing with dilute aqueous alkali and water and recrystallization from various organic solvents.

The following examples illustrate the invention but are not to be construed as limiting.

Example J.-3,3 ethylenebis(6 tertiarybutyl 3,4 hydro 2H 1,3 benzoxazine) Sixty grams of paraformaldehyde (equivalent to two moles of HCHO), 1.0 gram of potassium hydroxide and milliliters of methanol were mixed together and heated with stirring to the boiling temperature (65 C.) to obtain a clear solution. The reaction vessel and contents were then cooled to room temperature, and 30.0 grams (0.5 mole) of ethylenediamine added portionwise thereto over a period of about 15 minutes. The addition was carried out with stirring and cooling and at a temperature of from 25 to 30 C. Upon completion of the addition, 150.2 grams 1 mole) of p-tertiary-butylphenol was added thereto over a 15 minute period. Following the addition,

the mixture was heated with stirring at the boiling tem perature (65 C.) and under reflux for 15 minutes. The reaction mixture was then cooled in an ice bath whereupon a heavy gummy oil separated in the reaction mixture. The oil was separated and 500 milliliters of aqueous 10 percent sodium hydroxide and 250 milliters of toluene were successively added with stirring thereto and the resulting heterogeneous mixture warmed to about 60 C. After the heating, the organic layer was decanted and thereafter successively Washed with aqueous 5 percent sodium hydroxide and water. The washed mixture was then fractionally distilled under pressure to a final temperature of C. at 25 millimeters pressure to remove low boiling constituents and obtain a 3,3'-e thylenebis (6 tertiary butyl 3,4 dihydro 2H 1,3 benzoxa- Zine) product as a dark red oily residue. 3,3'-ethylenebis(6 tertiary butyl 3,4 dihydro 2H 1,3 benzoxazine) has a molecular weight of 408.

Sixty grams of paraformaldehyde (equivalent to two moles of HCHO), 1.0 gram of sodium hydroxide and 250 milliliters of methanol were mixed together and heated with stirring to the boiling temperature to obtain a clear solution. The reaction vessel and contents were then cooled to room temperature and 30.0 grams (0.5 mole) of ethylenediamine added portionwise to the reaction mixture over a period of about 15 minutes. The addition was carried out with stirring and cooling and at a temperature of from 25 to 30 C. Upon completion of the addition, 108.0 grams (1.0 mole) of p-cresol was slowly added with stirring and the resulting mixture heated at the boiling temperature (65 C.), and under reflux for 15 minutes. The resulting mixture was then 4 fractionally distilled under reduced pressure to remove Example 5.--3,3'-hexamethylenebis(3,4-dihyziro-6- the alcohol and 250 milliliters of toluene added to the methyZ-ZH-LS-benzoxazine) residue. The toluene and water were thereafter removed by distillation under reduced pressure to obtain a 3,3- ethylenebis(3,4 dihydro 6 methyl 2H 1,3 ben- 5 C 2 zoxazine) product as a gummy solid residue. The latter )IFCHKCHMQHTILY was washed with aqueous 10 percent sodium hydroxide, CH? O and recrystallized from a petroleum hydrocarbon boiling H1 H2 at from 86 to 100 C. The recrystallized product was found to melt at 1l2-114 C. 10 In the manner of Example 4, paraformaldehyde (60 Example 3.-3,3-ethylbenebis[3,4-dihydr0-6-(1,1,3,3- tetramethylbutyl)-2H-1,3-benz0xazine] (Inn our 0H on; onsoorn-o OHz( JOH CH3 OH: H1 H2 CH3 CH3 Sixty grams of paraformaldehyde (equivalent to two grams; 2 mole equivalents of I-ICHO), sodium hydroxide moles of HCHO), 1.0 gram of potassium hydroxide and (1 gram) and 250 milliliters of methanol were mixed 250 milliliters of methanol were mixed together and together and heated with stirring at the boiling temperaheated with stirring to the boiling temperature to obtain 25 ture to obtain a clear solution. The reaction vessel and a clear solution. The reaction vessel and contents were contents were cooled to room temperature and 58.2 grams then cooled to room temperature and 30.0 grams (0.5 of 1,6-hexamethylenediamine added over a period of mole) of ethylenediamine added to the reaction mixture minutes. The addition was carried out with stirring and over a period of about 15 minutes. The addition was cooling and at a temperature of between and C. carried out with stirring and cooling and at a tempera- 3 Thereafter, 108 grams (1.0 mole) of para-cresol was ture of from to p Completion of addiadded slowly and with stirring and the resulting mixture tion, 206.3 grams (1.0 mole) of p-(l, y heated at the boiling temperature and under reflux for Y P was Slowly added stirring and the 2 hours. The desired product was separated in exactly suiting mixture heated at the boiling temperature the same manner as described in Example 3 to obtain a reflux p 15 minutes The resulting 3,3'-hexamethylenebis(3,4-dihydro-6-methyl-2H-1,3-benzreact1on m xture was distilled under reduced pressure Oxazine) product as an oily liquid residue to remove the solvent and 250 millihters of toluene then added thereto. The toluene mixture Was washed with methyleneblsl34idlhydm'6' methyl-21143 binzoxazme) aqueous 10 percent sodium hydroxide and concentrated has a mfractfve Index n/ D of 15651 at 25 and a by distillation under reduced pressure to obtain a 3,3- 0 molecular welght of ethylenebis(3,4- dihydro-6- 1,1,3,3- tetrarnethylbutyl- 2H- The new compounds have been tested and found efie l,3benzoxazine) product as a semi-solid residue. This five as Pa a iC d F01 u h us th products may be product was recrystallized from ethyl acetate. The recrysdispersed on an inert finely divided solid and employed tallized product was found to melt at 144-145 C. as dusts. Also, such mixtures may be dipersed in water Example 4.3,3-hexamezhylenebis(6-cycl0hexyl-3,4- dihydro-ZH-l ,3-benzoxazine) Sixty grams of paraformaldehyde (equivalent to two with the aid of a wetting agent, and the resulting aqueous moles of HCHO), 1.0 gram of potassium hydroxide and suspensions employed as sprays. In other procedures, the 250 milliliters of methanol were mixed together and products may be employed as constituents of oil-in-water heated wtih stirring to the boiling temperature to obtain emulsions, or water dispersions with or without the addia clear solution. The reaction vessel and contents were tion of wetting, dispersing or emulsifying agents. In repthen cooled to room temperature and 58.2 grams (0.5 resentative operations, 3,3'-ethylenebis(6-tertiary-butylmole) of 1,6-hexanediamine added portionwise to the 3,4-dihydro-2H-1,3-benzoxazine) was dispersed in an reaction mixture over a period of about 15 minutes. The aqueous suspension f spores f F i oxysporium addition was carried outwith stirring and cooling and at lywpersici in an amount ffi i to supply 10 Pal-ts b a of from 250 to 300 UPOn Complenon weight of toxicant per million parts by weight of aqueous of the addmon 1769 grams mole) of p'cyclohexyl' suspension. Twenty-four hours later, the treated aquephenol was slowly added with stirring and the resulting OHS Sus d pension an an untreated check suspension of the on processed as described in Example 3 to obtain a 3,3-hexamcubated at 25 After three days of mcubatlon methylenebis(6 cyclohexyl 3,4 dihydm benzox servations showed a substantially complete control of the azine) product as a liquid residlm 3 3Lh th 1 fungal organism treated with 3,3:-ethyleneb1s(6-tert1arybis(6-cyclohexyl-3,4-dihydro-2I-I-l,3-benzoxazine) has a Y Y At the time Of refractive index n/ D of 1.5497 at 25 C. and a molecular the observation the check cultures were found to support weight of 516. a heavy growth of the Fusarium oxysporium lycopersici.

asaasv I claim: 1. A 3,3-alkylenebis(6-alkyl-3,4-dihydro-2H-1,3- benzoxazine) having the formula wherein R represents a member selected from the group consisting of alkyl radicals having from 1 to 8 carbon atoms, inclusive, and cyclohexyl, and n is an integer from 2 to 6, inclusive.

2. 3,3'-ethylenebis(6-tertiary-butyl-3,4-dihydro-2H-1,3- benzoxazine).

3. 3,3'- ethylenebis(3,4- dihydro-G-methyl-ZH-1,3-benzoxazine).

4. 3,3'- ethylenebis 3,4-dihydro-6- (1,1,3,3- tetramethylbutyl) -2H- 1,3 -b enzoxazine.

5. 3,3'-hexamethylenebis(6-cyc1ohexyl-3,4-dihydro-2H- 1,3-benzoxazine).

6. 3,3'-hexamethylenebis(3,4-dihydro-6-methyl-2H-1,3- benzoxazine) 7. A method for the preparation of a 3,3-alkylenebis(6- alky1-3,4-dihydro-2H-1,3-benzoxazine) having the formula wherein R represents a member selected from the group consisting of cyclohexyl and the alkyl radicals containing from 1 to 8 carbon atoms, inclusive.

References Cited in the file of this patent Burke et al.: J. Am. Chem. Soc., 74, 1518-20 (1952). 

1. A 3,3''-ALKYLENEBIS(6-ALKYL-3,4-DIHYDRO-2H-1,3- BENZOXAZINE) HAVING THE FORMULA 